Modified halogenated alumina catalyst for isomerizing saturated hydrocarbons

ABSTRACT

A catalyst comprising (a) a carrier mainly consisting of alumina, (b) an aromatic compound substituted with at least 2 hydroxy, oxo or hydrocarbyloxy groups and (c) halogen, and optionally, but preferably, containing a metal. It may be used for isomerizing saturated hydrocarbons at low temperature over long periods.

United States Patent [191 Torck et a1.

[ MODIFIED HALOGENATED ALUMINA CATALYST FOR ISOMERIZING SATURATEDHYDROCARBONS [75] Inventors: Bernard Torck, Boulogne-sur-Seine;

Michel Derrien, Rueil-Malmaison; Jean-Pierre Franck, Boug ival, all ofFrance [73] Assignee: lnstitut Francais du Petrole, des

Carburants et Lubrifiants, Rueil-Malmaison, France 22 Filed: 0a. 25,1972 211 App]. No.: 300,587

[30] Foreign Application Priority Data Oct. 29, 1971 France 71.39151[52] US. Cl. 252/429 R, 260/666 P, 260/683.7, 260/683.76 [51] Int. Cl.C07c 5/28 [58] Field of Search 252/429 R; 260/683.76, 260/683.68

[451 Mar. 11, 1975 Primary Examiner-Patrick P. Garvin Attorney, Agent,or Firm-Millen, Raptes & White [57] ABSTRACT A catalyst comprising (a) acarrier mainly consisting of alumina, (b) an aromatic compoundsubstituted with at least 2 hydroxy, 0x0 or hydrocarbyloxy groups and(c) halogen, and optionally, but preferably, containing a metal. It maybe used for isomerizing saturated hydrocarbons at low temperature overlong periads.

15 Claims, N0 Drawings MODIFIED HALOGENATED ALUMINA CATALYST FORISOMERIZING SATURATED HYDROCARBONS This invention concerns anew'catalyst and its use in those reactions of hydrocarbon conversion,which require a catalyst having a very active and selective acidity.Particularly this invention concerns a catalyst comprising a compositionof alumina, halogen and aromatic compound substituted with at least twohydroxy (OH), hydrocarbyloxy and/or x0 (=0) groups. The catalyst mayalso comprise a metal or a metal compound of the groups VI and/or VIIIof the periodic classification.

The invention also concerns the use of this catalyst for isomerizingsaturated or naphthenic hydrocarbons at a relatively low temperature theresulting isomerizates are attractive additives for manufacturinggasolines of high octane rating.

At high temperature, i.e., higher than 300C, the isomerization of the CC and C hydrocarbons may be carried out with conventional catalysts ofthe platinum-alumina type having a chlorine content of about 1 percent.As the thermal stability of the isoparaffins decreases as thetemperature increases, the content of isoparaffins at the thermodynamicequilibrium corresponding to such temperatures is not sufficiently highfor'ohtaining product streams of high octane rating, so that it isnecessary to separate the n-paraffins and, if required, to recycle them.This reaction may also be carried out at a lower temperature by usingcatalysts containing aluminum chloride or compounds having analuminum-chlorine bond. It is known that very active catalysts may beobtained by admixing aluminum chloride with a platinum containingalumina or by introducing chlorine into a platinum-alumina catalyst soas to have a chlorine content of from 6 to 10 percent by weight.irrespective of the particular mode of introduction of aluminumchloride, these catalysts are by themselves relatively inactive or, inany case, quickly deactivate, so that a promoter such as hydrochloricacid or a compound able to provide hydrochloric acid, for example anorganic chloride, must be continuously injected into the feed charge inorder to maintain a constant catalytic activity. Hydrochloric acid isthus present in the outflow and particularly in the gas recyclingdevices, and may result in corrosion troubles if traces of water areintroduced into the plant. In any case, this continuous supply ofpromotor constitutes a constraint for the user.

It is shown in this invention that the catalyst obtained by thehereinafter described method has a lasting intrinsic activity and doesnot require the continuous supply of a promoter of catalyst activity,and particularly does not require the continuous supply of hydrochloricacid or' of compounds providing the same. Thus, the suppressing of thecontinuous supply of a volatile inorganic acid and substituting it withthe supply of an organic compound of low volatility, when manufacturingthe catalyst, is quite advantageous.

This invention concerns a process for converting hydrocarbons andparticularly a process for isomerizing saturated aliphatic or naphthenichydrocarbons in the presence of a solid catalyst comprising (a) acarrier mainly containing alumina, which may optionaly contain a metalor a metal compound having hydrogenation activity, selected from thegroups VI and/or VIII of the periodic classification, (b) a poly(hydroxy, hy-

drocarbyloxy and/or oxo) aromatic compound and (c) a halogen. Thehalogen may be introduced by wellknown methods of alumina halogenation.

The carrier mainly consists of alumina. The aluminas which are moreparticularly adapted to the manufacture of these catalysts are porousaluminas of high specific surface which contain hydrogen admittedlypresent in the form of hydroxy groups. For example. excellent resultsmay be obtained with aluminas manufactured by roasting ,B aluminatrihydrate such as bayerite or a mixture of this particular alumina withother roasted, alumina hydrates, although aluminas manufactured byroasting other alumina hydrates, such as a-alumina trihydrate orgibbsite, a-aluminas monohydrate or aluminae obtained by hydrolizingaluminum alcoholates may also be used. Such aluminas usually have a highspecific surface of from to 500 m /g or even more. The most activecatalysts are usually obtained when this surface is higher than 200 m /gand particularly higher than 300 m lg. This point, however. is not themost important, since the content of hydroxy groups, when addingchlorine, is also responsible of the catalyst activity. Thus the thermaltreatments, carried out at temperatures of from 250 to 800C formanufacturing aluminas, must be effected in such a manner that a highspecific surface and, above all, an optimum content of hydroxy groups beobtained.

It may be useful, in certain cases, to select, as the carrier, analumina having a content of one or more refractory oxides selected fromthe oxides of metals from groups II and V of the periodicclassification. Alumina may thus contain up to 50 percent by weight ofoxides, such as silicon, titanium, beryllium, zirconium or mag nesiumoxides.

Alumina preferably has a relatively low content of hydrogenating metalor metal compound from groups Vl or Vlll ofthe periodic classification.The preferred metal is selected from the platinum metal group and itscontent may range from 0.01 to 5 percent by weight and preferably from0.1 to 2 percent by weight. Platinum and palladium are particularlyconvenient metals of the platinum group. The catalyst may also containthe catalytic metals by pairs, for example platinumiridium,platinum-ruthenium, platinum-tungsten, platinum-thallium, the additionalmetals, when desired, being selected from other groups than the groupsVl and/or VIII. The metal must be as highly dispersed on the catalystsurface as possible, and the methods which give the required dispersionstate consist either of precipitating the metal of the platinum group inthe form of a sulfide, or of impregnating, for example withchloroplatinic acid, and favouring a homogenous impregnation by theaddition to the medium of compounds giving rise to a co-operativechemisorption on the carrier, thus favouring a better repartition of themetal on the catalyst surface. Although not imperative, it is preferredto carry out the reduction of the metal compound with hydrogen beforechlorinating the catalyst. A convenient carrier is a conventionalreforming catalyst.

This alumina-containing carrier, optionaly comprising a metal of theplatinum group, must contain an arcmatic compound having at least 2groups selected from the hydroxy, hydroearbyloxy and oxo groups.

The aromatic compound is, for example, a compound which complies withthe formula (R )m Ar (Z )x mum valence of Ar, Ar is an aromatic radicaland the m groups R, identical or different, are substituents, forexample halogen atoms or monovalent hydrocarbon radicals each,containing for example, from 1 to carbon atoms. The similar ordissimilar groups Z are selected from the group consisting of OH, O andOR, wherein R is a monovalent hydrocarbon radical, for example alkyl,preferably having 1-6 carbon atoms.

In these compounds, certain aromatic rings may be replaced by carboncontaining conjugated rings including heteroatoms, for example N or O. Amixture of compounds of these various types may also be used.

Preferably the aromatic compound contains at least one benzene ring andis of the general formula where the n groups Y may be, for example,alkyl, cycloalkyl or aryl groups, optionaly condensed with the benzenering, or electronegative groups such as chlorine or other halogen. Forexample Y may be methyl, ethyl, npropyl, iso-propyl, n-butyl, iso-butylor tert. butyl n is an integer of 0,l,2,3 or 4.

The following compounds containing one benzene ring are examples ofcompounds containing at least one benzene ring substituted with at leasttwo hydroxy or oxo groups pyrocatechol, resorcinol, hydroquinone,

benzoquinone, quinhydrone and their substitution de- I rivatives: 3,4dihydroxy toluene, the chloro, fluoro and bromo resorcinols, the chloro,fluoro and bromo hydroquinones, the chloro, fluoro and bromoquinones,for example 4 chlorocatechol, 4 -chloro resorcinol,tetrachlorohydroquinone, tetrafluorocatechol, chloranil,f1uoranil,2chloro 1,4 benzoquinone with respect to compounds containing severalbenzene rings 1,3 -dihydroxy naphthalene, 2,3 dihydroxy naphthalene, 1.3dihydroxy 5,7 -naphthalene disulfonic acid, 1,2 dihydroxy anthracene,3,4 dihydroxy phenanthrene. 2,5 dimethyl 1,4 naphthoquinone, 6 -bromo1,4 dihydroxy 9,10 anthraquinone, 1,4 -anthraquinone, acenaphthencquinone, alizarine, chloranilic acid, 1,2,7 trihydroxy 9,10anthraquinone.

This carrier of platinum and alumina must have a content of halogen,particularly chlorine, in addition to the aromatic compound. The amountof halogen added to the catalyst may range from 1 to 20 percent byweight and particularly from 4 to 12 percent, the optimal amountdepending on the specific surface of the carrier. It is well-known thatalumina may be chlorinated with chlorinated hydrocarbons since it is amethod for manufacturing aluminum chloride from alumina. When themanufacture of an active catalyst of acceptable life time, bychlorination of a carrier of platinum and alumina, is contemplated, itis known that this chlorination must be carried out in controlledmanner, particularly so as to avoid the formation of aluminum chloridesince the latter sublimates at 180C. That is why, in these conventionalchlorinations, the choice of the chlorinated hydrocarbon is of majorimportance.

It has been observed in this invention that, when the catalyst isimpregnated with a polyhydroxy polyalkoxy or polyoxoaromatic compound,the chlorination may be carried out to a larger extent withoutsublimation of aluminum chloride and carrying away from the chlorinationreactor during the treatment. It is thus shown in the invention that thecarrier may be chlorinated to a larger extent and that the chlorinationtakes place much more smoothly at the catalyst surface. Thus anychlorinated hydrocarbon may be chosen for carrying out thischlorination, the choice being finally dependent on the amount ofchlorine which must be introduced into the catalyst since certainhydrocarbons are more strongly chlorinating than others. The process isthus conducted in the presence of reducing compounds, i.e., thepolyhydroxyaromatic compounds.

It is shown that it is preferred to effect this chlorination afterimpregnation of the polyhydroxy polyalkoxy or polyoxo aromatic compound,although this is not imperative a good catalyst may also be obtained byintroducing the aromatic compound after chlorination of alumina.

This chlorination may be carried out in the presence of the abovereducing compounds by means of chlorinated hydrocarbons, for examplecarbon tetrachloride, carried along with an inert or oxidizing gas.Examples of gases to be used in this chlorination are nitrogen, oxygenand air; this chlorination may be carried out at a temperature of, forexample, to 600C.

Other halogenation agents, previously proposed for manufacturingisomerization catalysts containing halogen, may be used, for example,gaseous halogens and inorganic gaseous halogen compounds, for exampleSOCI SO Cl S Cl ;chloroform, methylene chloride and hexachloroethane areexamples of organic compounds.

The impregnation of the catalyst with a poly (hydroxy, hydrocarbyloxy or0x0) aromatic compound may be carried out according to conventionalimpregnation techniques, for example by contacting the catalyst with asolution of the selected compound in a convenient solvent, for examplewater, a chlorinated hydrocarbon or a saturated or unsaturatedhydrocarbon. After impregnation, the catalyst may contain from 0.001 to20 percent and preferably from 0.01 to 10 percent by weight of aromaticcompound.

The introduction of the aromatic compound may be effected during thechlorination by using a solution of this compound in the chlorinatingagent or by stripping the said compound in the inert gas employed forthe chlorination.

The catalyst may also be first chlorinated and the aromatic compound isintroduced thereafter as a solution in the isomerizable hydrocarbon.

This invention thus concerns a catalyst manufactured in the above mannerand also the use ofthis catalyst for isomerizing saturated hydrocarbons,particularly for isomerizing aliphatic or naphthenic hydrocarbons, so

' as to obtain products of higher octane number than the feed and whichmay be used in fuels, i.e., branched or unbranched aliphatic ornaphthenic hydrocarbons, C, or higher, having a boiling point lower than200C, particularly the aliphatic or naphthenic hydrocarbons of 4 7carbon atoms per molecule, for example n-butane, n-pentane, n-hexane,methylpentanes, methyl cyclopentane, cyclohexane, heptane or theirmixtures. if only the n-paraffins are to be isomerizcd, the feed may bepreviously treated for separating n-paraffins from the otherhydrocarbons by using separation techniques such the molecular sieves.Topping products from the straight distillation, light naphtha fractionsand hydrogenated light fractions from steam-cracking are examples ofindustrial containing these hydrocarbons.

drocarbons may be maintained in the reactor either in the liquid stateor in the gas state and the reaction may be carried out a pressure offrom 1 atm. to 150 kg/cm preferably from 10 to 70 kg/cm2. The reactionmust be carried out in the presence of hydrogen whith a molar ratio ofthe hydrogen to the hydrocarbon of, for example, from 0.01 to 20 andpreferably from 1.5 to 10. The space velocity concerning theintroduction of hydrocarbon into the reactor is selected from 0.01 to 20and preferably from 1.5 to 10. The space velocity concerning theintroduction of hydrocarbon into the reactor is selected from 0.05 to 10v. V. b, preferably 0.2 to 5 v. v. h.

The charge is preferably made free of sulfur, water and aromatichydrocarbons.

The manufacture of the catalyst and its use for isomerizing paraffins atlow temperature are illustrated by the following examples EXAMPLE 1 100g of a conventional reforming catalyst consisting of alumina containing0.35 percent by weight of platinum and 0.4 percent by weight of chlorineare introduced into an isomerization reactor and heated up to 200C anitrogen stream is passed therein at an hourly rate of 600 liters perliter of catalyst. Nitrogen is then saturated with carbon tetrachloride.25 ccm of CCl are passed in that way within 2 hours at the same nitrogenEXAMPLE 2 100 g of a conventional reforming catalyst consisting ofalumina containing 0.35 percent. b.\\'. of platinum and 0.4 percent b.w.of chlorine are impregnated with a pyrocatechol solution in chloroformat room temperature. in order to have a pyrocatechol content of 3percent by weight'after chloroform evaporation. The catalyst is thenintroduced into the isomerization reactor which is heated up to 200C ina nitrogen stream. The catalyst is then contacted with carbontetrachloride carried along with a nitrogen stream whose hourly feedrate is 600 liters per liter of catalyst. 25 cc of carbon tetrachlorideare thus introduced in 2 hours. The reactor is then heated up to 300Cand 25 cc of carbon tetrachloride are introduced again in 2 hours withthe same' nitrogen feed rate. The resulting catalyst then contains 035percent b.w. of platinum and l 1 percent b.w. of chlorine. n-pentane isisomerized with the so treated.- catalyst. The test conditions are thefollowing lsomerization temperature 150C Reactor pressure 20 Kg/em2Molar ratio H lhydrocarbon 4 Space velocity l v.v.h.

Water content of n-pentanc 20 ppm The products have been analysed byvapor phase chromatography and found to have the following composition(Table 11) TABLE 11 Time in hours Charge 10 20 50 100 300 Product '7!weight Hydrocarbons C,-, 0.05 0.1 0.15 0.12 0.10 0.10 lsopentane 0.436.0 44.0 60.0 58.0 59.0 npentane 99.1 63.57 55.55 39.59 41.61 40.6Cyclopentane 0.5 0.33 0.30 0.29 0.20 0.30

rate. The resulting catalyst contains 0.34 percent b. w. EXAMPLE 3 ofplatinum and 10.5 percent b. w. of chlorine npentane is isomerized withthis catalyst under the following conditions lsomerisation temperature150C Reactor pressure 20 Kg/em2 Molar ratio H lhydrocarbons 4 Spacevelocity 1 v.v.h. Water content of n-pentane 20 ppm The products havebeen analysed by vapor phase chromatography and found to have thefollowing composition (Table l) TABLE 1 Time in hours Charge 10 15 20 3050 Product 2 weight Hydrocarlmns 0.05 0.12 0.06 0.05 0.05 0.04lsopentanc 0.4 8.38 10.52 1 1.83 11.94 11.89 n-pentane 99.1 91.22 89.1987.90 87.77 87.83 Cyclopentane 0.5 0.28 0.23 0.22 0.24 0.24

TABLE 111 Time in Product hours Charge 10 20 30 50 "/1 weightHydrocarbons C 0.05 0.15 0.17 0.15 0.12 0.10 lsopcntanc 0.4 45.0 55.0 h1.2 614.3 72.5 n-pentane 99.1 54.55 44.5 38.3 31.3 27.1 Cyclopentane 0.50.3 0.33 0.35 0.28 0.30

EXAMPLE 4 lsopentane 17.0 1 n-pentane -t\.0 '1 100g of a conventionalreformrngcatalyst consisting lsohexanes 24.7 i

I I a 1 alumina containing 0.35 percent b.w. of platinum and 0.35percent b.w. of chlorine are impregnated with a Hcpumc A solution oftetraehlorohydroquinone in chloroform at 5 d h 1 Id l l It" .1- Z17.room temperature so as to have a tetrachlorohydroqur- ,';,',,Z ifi 3 7.5,! Us none content of 1.5 percent b.w. after chloroform g ffif giwmcrimm 011C101 13"?) 1 O FOSSLII'C WI m C reactor 1 C111- evaporation.The catalyst 18 matntarnedat 150 C for 2 Molar m0 of H2 [he hydmmrhuns 4hours in a nitrogen stream. The catalyst 15 then charged Feed rate ofthe light gasoline 1 \,\'.h. into the isomerization reactor which isheated up to [0 wmelwmcmol feed m 200C in a nitrogen stream.

Chlorination is carried out in the same way as in the The results areSummanzed Table V wh'ch 'Y fomgoing examplei mPemane is isomerized underthe the percent of the selected aromatic compound with following testConditions respect to the catalyst and the analysis of the effluent 15after 50 and 100 hours of run. (Table V).

Isomerizution temperature 110C EXAMPLE l7 fii f f f f tffi f f i Kg/cmz100 g of a catalyst consisting of alumina having a cong i Z tent ofry-alumina higher than 60 percent and a surface 20 of 300 m andcontainin 0.35 ercent b wei ht of g g Y g The products have beenanalysed by vapor phase platinum are introduced into the isomerrzatronreactor chromatography and found to have the composition and heated upto 280C under a nitrogen stream whose given in Table IV. feed rate is600 liters per liter of catalyst per hour.

TABLE IV Time in hours Charge 10 50 Product '71 weight Hydrocarbons C0.05 0.20 0.20 0.15 0.1 [sopeutane 0.4 30.0 35.5 40.0 45.5 n-pentane99.1 69.5 63.97 59.55 54.1 Cyclopentane 0.5 0.3 0.33 0.3 0.3

EXAMPLES 5 to 16 After 1 hour of stripping with nitrogen, carbon tetra-100 g of a Catalyst consisting of alumina having an chloride isadmitted. 30 cc of CCl, are thus introduced n-alumina content ofabout 80percent by weight, a sur- 1 r w g g catalyst: g f face of 400 m /g and aplatinum content of 0.3 percent 0 i g g" g C (0 percent in example 16)are impregnated with a solu- 40 g 2 28??? t y??? tion of a polyhydroxy,polyoxo-or polyalkoxyaromatic f: i mtrogcn e y i compound in chloroformat room temperature, so as to 50 0 enzoqumonc m pen 1' Supply Saidalumina with an amount of aromatic ter)1s also introduced at a rate of100 cc per hour. -00 pound which. after solvent evaporation, is the sameas f' of i Solutl0n are thuslmssefj thcrcthroughf The the percentage byweight with respect to the catalyst i lf l of l calmed out accordmg mwhich is given in table V. The catalyst is then charged t c Onowmg testCondltmm into the isomel'lzutlon reactor whlch ls brought to Temperaturewithin the isomerization :120( 200C under nitrogen stream. Carbontetrachloride, Preactor l h t ressure wltiin t e reactor 20 KG/cm2 f-Along with mtrogen feed rate Molar ratio H. ./hydrocarhon 3 per liter ofcatalyst per hour, 15 introduced therein. 18 (2, feed rate (v.v.h.) 1liquid vulumc cc of CC], are thus introduced in 1 hour. The reactor P910 m temperature is then raised to 280C with the same ni-- pp trogenfeed rate and 18 cc ofCCl are introduced again The products have beenanalysed by vapor phase in 1 hour. A light gasoline of the followingcomposition chromatography and found to have the composition by weightsummarized in Table VI.

TABLE VI Time in hours Product "/1 b.w. Charge 10 20 40 I20 HydrocarbonsC,, 0.05 0.15 025 0.27 030 0.20 lsopentane 04 36.0 46.0 55.2 60.3 60.0N-Pentane 89.1 63.53 53.4 44.2 39.2 39.5 Cyclopentane 0.5 0.32 0.35 0.330.20 0.21

TABLE V N Amoung Analysis of the effluent Analysis of the effluentExample Nature of the compound /0 b.w. after 50 h after 100 h C. /riso C/riso C. C /1 "/(iso C /iiso C].

5 It .1 s

5 Resorcinol 1.1 0.25 75.5 87.3 0.20 75.6 87.2 6 Chlorohydroquinone 1.60.35 72.5 82.5 0.25 73.0 83.0 7 Fluoranil 3.0 0.20 70.5 78.0 0.15 69.077.0 8 Chloranilic acid 4.0 0.15 71.0 81.5 0.15 72.0 82.0 9 Pyrogallol2.5 0.10 70.5 79.5 0.10 71.5 80.0 10 2.3 Dihydroxy naphthalene 0.5 0.1558.5 67.5 0.10 57.5 67.0 1 I Antranquinone 5.0 0.10 57.0 68.0 0.10 58.569.5 12 Alizarine 3.5 0.35 72.5 86.0 v 0.25 74.0 86.5 13 1.2.7trihydroxy 9.10

antranquinone 6.0 0.15 58.5 68.5 0.10 58.0 68.6 14 1.2.3 trlmethoxybenzene 3.0 0.25 68.5 78.0 0.15 71.0 810 15 4 Methoxy phenol 2.0 0.2065.0 72.5 0.15 70.5 80.0 15* 4 Methoxy phenol 2.0 0.80 62.0 71.0 0.8560.5 70.0

" Catalyst without platinum EXAM PLE l8 lene l-hydroxy -3-methoxynaphthalene and 4,5-

50 g of a conventional reforming catalyst consisting of y alumina whosespecific surface is 250 m /g and containing 0.34 percent b.w. ofplatinum are introduced into an isomcrization reactor and heated up to280 C in a nitrogen stream whose feed rate is 600 liters per liter ofcatalyst and per hounAfter 1 hour of nitrogen stripping. there isintroduced a 5 percent b.w. solution of 1.2 dimethoxy benzene in carbontetrachloride at a feed rate of 12 cc per hour. After nitrogen strippingat 290 C, the temperature is lowered to 150 C and nitrogen issubstituted whith hydrogen. The isomerization of n-pentane is carriedout under the following Conditions:

Temperature of the isomerization reactor 150 C Pressure within thereactor Kg/cm Molar ratio H /hydrocarhons 2.5

n-C feed rate l v.v.h. Water content o1- the n C.-. 10 p.p.m.

The products have been analysed by vapor phase chronmtography and foundto have the composition stated in Table V11 dihydroxy-7-methoxyanthraquinone.

What we claim as our invention:

1. In a process for manufacturing a catalyst. wherein alumina compositedwith a platinum group metal is halogcnated with a halogen compoundselected from the group consisting of chlorinated hydrocarbon. chlorine.SOCl SO Cl and S Cl to form a composite consisting essentially ofalumina, about l20 percent by weight of halogen. and about 0.01-5percent by weight of said platinum group metal. the improvement of alsocompositing with said alumina an aromatic compound of the formula (Rln,I (Z) where x is an integer of at least 2, m is zero or an integer, (xin) being at most the maximum valence of Ar, Ar is an aromatichydrocarbon radical containing at least one carbocyclic ring. the ingroups R are independently halogen atoms or monovalent hydrocarbonradicals and the x groups Z are independently hydroxy. oxo orhydrocarbyloxy. the aromatic compound content of said composite beingabout 0.00l-20 percent by weight.

2. The process of claim 1, wherein alumina is composited first with theplatinum group metal and then with the aromatic compound.

3. The process of claim 1, wherein alumina is com- TABLE Vll Time inhours Products a b.\\'. Charge 10 20 Hydrocarbons C; 0.05 0.12 0.15 0.170.20 0.22 lsopentane 0.4 30.0 42.3 50.8 55.1 55.3 n-pentane 99.1 69.457.2 48.7 44.4 44.08 Cyclopentane 0.5 0.48 0.35 0.33 0.30 0.30

posited first with the platinum group metal. then with the aromaticcompound and finally with the halogen compound.

4. The process of claim 1, wherein the carbocyclic ring of said aromaticcompound is the carbocyclic ring of benzene. naphthalene, anthracene,phenanthrenc or acenaphthene.

5. The process of claim 1, wherein x is 2 to 4.

6. The process of claim 1, wherein the halogen compound is a chlorinatedhydrocarbon.

7. The process of claim I, wherein the halogen compound is selected fromthe group consisting of methylene chloride, chloroform and carbontetrachloride.

8. A process as defined by claim 1 wherein said aromatic compound is ofthe formula:

halogen n is hydroxy toluene, 2-isopropyl Y hydrm uinone diethylether,chloropyrocatechol dimcthyl ether, lluoro resorcinol dimethyl ether,bromo hydroquinonc dimethyl ether, phloroglucinol trimethyl ether,pyrogallol trimethyl ether, 2,3-dimethoxy phenol. 2,3,4- trimethoxyphenol, 2,3-dimcthoxy naphthalene, 1- hydroxy-3-methoxy naphthalene and4,5-dihydroxy-7- methoxy anthraquinone.

10. A process as defined by claim 9 wherein the amount of aromaticcompound is by weight 0.0! to 10 percent and the halogen is 4 to 12percent.

11. A catalyst as produced by the process of claim 1.

12. A catalyst as produced by the process of claim 3.

13. A catalyst as produced by the process of claim 7.

14. A catalyst as produced by the process of claim 9.

'15. A catalyst as produced by the process of claim 10.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO.3,870,653

DATED March 11, 1975 INVENTO I Torck, Bernard; D'errien, Michel; et a1It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

ISEAL] T ble 11; number down from "100" and across from "cyclopentane"should be changed from ".020" to -0.29-.

Column 7, line 1, after the word "consisting" insert Table V "11Antranquinone" should be changed to -ll Anthranquinone--. SAMECORRECTION FOR "13" last line "15 4 Methoxy phenol" should be changed to-l6 4 Methoxy phenol In Tables I, III, IV under charge, across from"Hydrocarbons C5" change "$0 .05" to 0.05-'

Column 2, line l5, delete --sfrom the word "B-aluminas" Column 2, line32, the word "and should be changed to 2, line 53, the word "homogenous"should be changed to "homogeneous".

2, line 67 (Z) )X" should be changed to-- (Z)X--.

4, line 67 "mixtures" should follow "industrial", before "containing".

5, line 7, --at-- should follow "out" before "a". 6, line 30, "Watercontent of n-pentane 20 ppm" should be on separate line below "spacevelocity note the sign should be as in original Signed and Scaled thissecond Day of December1975 Column Column Column Column Column A ttest:

RUTH C. MASON Arresting Officer C. MARSHALL DANN Commissioner uflatemsand Trademarks

1. IN A PROCESS FOR MANUFACTURING A CATALYST, WHEREIN ALUMINA COMPOSITEDWITH A PLATINUM GROUP METAL IS HALOGENATED WITH A HALOGEN COMPOUNDSELECTED FROM THE GROUP CONSISTING OF CHLORINATED HYDROCARBON, CHLORINE,SOCL2, SO2CL2 AND S2CL2, TO FORM A COMPOSITE CONSISTING ESSENTIALLY OFALUMINA, ABOUT 1-20 PERCENT BY WEIGHT OF HALOGEN, AND ABOUT 0.01-5PERCENT BY WEIGHT OF SAID PLATINUM GROUP METAL, THE IMPROVEMENT OF ALSOCOMPOSITING WITH SAID ALUMINA AN AROMATIC COMPOUND OF THE FORMULA (R)MAR (Z)X WHERE X IS AN INTEGER OF AT AT LEAST 2, M IS ZERO OR AN INTEGER,(X + M) BEING AT MOST THE MAXIMUM VALENCE OF AR IS AN AROMATICHYDROCARBON RADICAL CONTAINING AT LEAST ONE CARBOCYCLIC RING, THE MGROUPS R ARE INDEPENDENTLY HALOGEN ATOMS OR MONOVALENT HYDROCARBONRADICALS AND THE X GROUPS Z ARE INDEPENDENTLY HYDROXY OXO ORHYDROCARBYLOXY, THE AROMATIC COMPOUND CONTENT OF SAID COMPOSITE BEINGABOUT 0.001-20 PERCENT BY WEIGHT.
 1. In a process for manufacturing acatalyst, wherein alumina composited with a platinum group metal ishalogenated with a halogen compound selected from the group consistingof chlorinated hydrocarbon, chlorine, SOCl2, SO2Cl2 and S2Cl2, to form acomposite consisting essentially of alumina, about 1-20 percent byweight of halogen, and about 0.01-5 percent by weight of said platinumgroup metal, the improvement of also compositing with said alumina anaromatic compound of the formula (R)m Ar (Z)x where x is an integer ofat least 2, m is zero or an integer, (x + m) being at most the maximumvalence of Ar, Ar is an aromatic hydrocarbon radical containing at leastone carbocyclic ring, the m groups R are independently halogen atoms ormonovalent hydrocarbon radicals and the x groups Z are independentlyhydroxy, oxo or hydrocarbyloxy, the aromatic compound content of saidcomposite being about 0.001-20 percent by weight.
 2. The process ofclaim 1, wherein alumina is composited first with the platinum groupmetal and then with the aromatic compound.
 3. The process of claim 1,wherein alumina is composited first with the platinum group metal, thenwith the aromatic compound and finally with the halogen compound.
 4. Theprocess of claim 1, wherein the carbocyclic ring of said aromaticcompound is the carbocyclic ring of benzene, naphthalene, anthracene,phenanthrene or acenaphthene.
 5. The process of claim 1, wherein x is 2to
 4. 6. The process of claim 1, wherein the halogen compound is achlorinated hydrocarbon.
 7. The process of claim 1, wherein the halogencompound is selected from the group consisting of methylene chloride,chloroform and carbon tetrachloride.
 8. A process As defined by claim 1wherein said aromatic compound is of the formula: Yn C6 H4 n(Z)2 whereinY is alkyl, cycloalkyl aryl, or halogen n is 0,1,2,3, or
 4. 9. A processas defined by claim 1 wherein the aromatic compound is selected from thegroup consisting of pyrocatechol, tetrachlorohydro-hydroquinone,benzoquinone, resorcinol, chlorohydroquinone, fluoranil, chloranilicacid, pyrogallol, 2,3 dihydroxy naphthalene, anthraquinone, alizarine,1,2,7 trihydroxy 9,10 anthraquinone, 1,2,3 trimethoxy benzene, 4 methoxyphenol, 1,2-demethoxy benzene, 4-chloro-1,2-benzoquinone,2,5-dimethyl-1, 4-benzoquinone, pyrogallol, hydroxyquinol,phloroglucinol, 9,10-dihydroxy anthracene, 1,2, 10trihydroxy anthracene,9,10-phenanthraquinone, 9,10-anthraquinone, 2-methoxy phenol, 3-methoxyphenol, pyrocatechol dimethylether, hydroquinone dimethylether,3-methoxy-4-hydroxy toluene, 2-isopropyl hydroquinone diethylether,chloropyrocatechol dimethyl ether, fluoro resorcinol dimethyl ether,bromo hydroquinone dimethyl ether, phloroglucinol trimethyl ether,pyrogallol trimethyl ether, 2,3-dimethoxy phenol, 2,3,4-trimethoxyphenol, 2,3-dimethoxy naphthalene, 1-hydroxy-3-methoxy naphthalene and4,5-dihydroxy-7-methoxy anthraquinone.
 10. A process as defined by claim9 wherein the amount of aromatic compound is by weight 0.01 to 10percent and the halogen is 4 to 12 percent.
 11. A catalyst as producedby the process of claim
 1. 12. A catalyst as produced by the process ofclaim
 3. 13. A catalyst as produced by the process of claim
 7. 14. Acatalyst as produced by the process of claim 9.